Organometallic complex, and preparation method and use thereof

Abstract

Provided are: a novel organometallic complex useful as an active ingredient of a bactericide applied to agricultural and horticultural crops; and a preparation method thereof.　The novel organometallic complex comprises triflumizole, metal cations, and organic acid anions.　The organometallic complex can be prepared by mixing triflumizole and / or a salt thereof with at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.　Examples of the metal elements of the metal cations include zinc, copper, magnesium, calcium, nickel, cobalt, iron, and manganese.

Description

Organometallic complexes, and methods for producing and using the same

[0001] The present invention relates to an organometallic complex, and a method for producing and using the same. More specifically, the present invention relates to an organometallic complex useful as an active ingredient in a fungicide applied to agricultural and horticultural crops, and a method for producing and using the same. This application claims priority to Japanese Patent Application No. 2023-217302, filed December 22, 2023, the contents of which are incorporated herein by reference.

[0002] Organometallic complexes are used as catalysts for various chemical reactions, including amidation reactions. For example, Patent Document 1 discloses a zinc-imidazole-carboxylate complex that catalyzes a urethane reaction and can be produced by reacting zinc(II) biscarboxylate with an imidazole compound.

[0003] Patent Document 2 discloses a zinc complex represented by formula (A) which is useful as a synthesis catalyst.

[0004] On the other hand, compounds containing an imidazole group are useful as active ingredients of fungicides applied to agricultural and horticultural crops. For example, Patent Document 3 discloses a compound containing an imidazole group represented by formula (B). Patent Document 3 also describes agriculturally acceptable salt forms of this compound, including hydrochloride salts, sulfate salts, metal salts, and addition complexes of compounds such as iron, chromium, and zinc.

[0005] Patent Document 4 discloses azolylmethyloxiranes (for example, epoxiconazole) represented by formula (C) and plant-tolerable acid addition salts and metal complexes thereof.

[0006] Special Publication No. 2014-510174 WO 2014 / 157524 A1 Japanese Patent Application Publication No. Hei 7-285943 Publication No. 4-74355

[0007] Triflumizole is easily decomposed by acids and bases and has a low melting point, making it difficult to formulate. The present invention aims to provide a novel organometallic complex useful as an active ingredient in fungicides applied to agricultural and horticultural crops, as well as a method for producing the same.

[0008] The present invention includes the following aspects.

[0009] [1] An organometallic complex comprising triflumizole, a metal cation, and an organic acid anion. [2] The organometallic complex according to [1], wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron, and manganese. [3] The organometallic complex according to [1] or [2], wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and a tautomer thereof, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and a tautomer thereof, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

[0010] [4] A method for producing an organometallic complex comprising triflumizole, a metal cation, and an organic acid anion, the method comprising mixing triflumizole and / or a salt thereof with at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.

[0011] [5] The method according to [4], wherein the molar ratio of the metal cation derived from the metal compound and the organic acid anion derived from the organic acid and / or organic acid salt is 0.5 to 2 mol per 1 mol of triflumizole derived from triflumizole and / or its salt. [6] The method according to [4] or [5], wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese. [7] The production method according to [4] or [5], wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

[0012] [8] A composition comprising triflumizole, an organometallic complex comprising a metal cation and an organic acid anion. [9] A composition comprising triflumizole, an organometallic complex comprising a metal cation and an organic acid anion, and water.

[0013]

[10] An agricultural and horticultural fungicide containing, as an active ingredient, an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion.

[0014] The organometallic complex of the present invention is less likely to volatilize, has a longer-lasting fungicidal effect, is less likely to cause phytotoxicity, and is less likely to stain agricultural and horticultural crops than triflumizole or its salt. The organometallic complex of the present invention is less difficult to formulate. The pesticide composition of the present invention has a high residual rate of triflumizole, the active ingredient of the fungicide applied to agricultural and horticultural crops, and therefore has a longer-lasting fungicidal effect.

[0015] FIG. 1 shows a diffraction chart of triflumizole. FIG. 2 shows a diffraction chart of zinc benzoate. FIG. 3 shows a diffraction chart of the solid product prepared in Example 1. FIG. 4 shows a diffraction chart of zinc diethyldithiocarbamate. FIG. 5 shows a diffraction chart of the solid product prepared in Example 2. FIG. 6 shows a diffraction chart of zinc N-ethyl-N-phenyldithiocarbamate. FIG. 7 shows a diffraction chart of the solid product prepared in Example 3. FIG. 8 shows a diffraction chart of zinc acetylacetonate. FIG. 9 shows a diffraction chart of the solid product prepared in Example 4. FIG. 10 shows a diffraction chart of zinc adipate. FIG. 11 shows a diffraction chart of the solid product prepared in Example 5. FIG. 12 shows a diffraction chart of zinc maleate. FIG. 13 shows a diffraction chart of the solid product prepared in Example 6. FIG. 14 shows a diffraction chart of zinc succinate. FIG. 15 shows a diffraction chart of the solid product prepared in Example 7. FIG. 16 shows a diffraction chart of zinc malonate. FIG. 17 shows a diffraction chart of the solid product prepared in Example 8. FIG. 18 shows a diffraction chart of zinc terephthalate. FIG. 19 shows a diffraction chart of the solid product prepared in Example 9. FIG. 19 shows a diffraction chart of zinc glutarate. FIG. 1 shows a diffraction chart of the solid product prepared in Example 10. FIG. 2 shows a diffraction chart of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt. FIG. 3 shows a diffraction chart of the solid product prepared in Example 11. FIG. 4 shows a diffraction chart of 2,6-pyridinedicarboxylic acid. FIG. 5 shows a diffraction chart of zinc oxide. FIG. 6 shows a diffraction chart of the solid product prepared in Example 12. FIG. 7 shows a diffraction chart of phthalic acid. FIG. 8 shows a diffraction chart of zinc chloride. FIG. 9 shows a diffraction chart of the solid product prepared in Example 13. FIG. 10 shows a diffraction chart of zinc dimethyldithiocarbamate. FIG. 11 shows a diffraction chart of the solid product prepared in Example 14. FIG. 12 shows a diffraction chart of benzoic acid. FIG. 13 shows a diffraction chart of copper(II) hydroxide. FIG. 14 shows a diffraction chart of the solid product prepared in Example 15. FIG. 15 shows a diffraction chart of the solid product prepared in Example 16. FIG. 16 shows a diffraction chart of the solid product prepared in Example 17.FIG. 1 shows a diffraction chart of the solid product produced in Example 18. FIG. 2 shows a diffraction chart of the solid product produced in Example 19. FIG. 3 shows a diffraction chart of terephthalic acid. FIG. 4 shows a diffraction chart of the solid product produced in Example 20. FIG. 5 shows a diffraction chart of maleic acid. FIG. 6 shows a diffraction chart of the solid product produced in Example 21.

[0016] The organometallic complex of the present invention comprises triflumizole, a metal cation, and an organic acid anion.

[0017] One embodiment of the method for producing an organometallic complex of the present invention comprises mixing triflumizole and / or a salt thereof with an organic acid metal salt. Another embodiment of the method for producing an organometallic complex of the present invention comprises mixing triflumizole and / or a salt thereof with an organic acid and a metal compound. Another embodiment of the method for producing an organometallic complex of the present invention comprises mixing triflumizole and / or a salt thereof with an organic acid salt and a metal compound.

[0018] Triflumizole is a compound known as the active ingredient of imidazole fungicides applied to agricultural and horticultural crops. Triflumizole is a compound represented by formula (I) ((E)-N-[4-chloro-2-(trifluoromethyl)phenyl]-1-(1H-imidazol-1-yl)-2-propoxyethan-1-imine).

[0019]

[0020] The salt of triflumizole is not particularly limited as long as it is agriculturally and horticulturally acceptable, and examples thereof include salts with inorganic acids such as hydrochloric acid and sulfuric acid; salts with organic acids such as acetic acid and lactic acid; salts with alkali metals such as lithium, sodium and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with other metals; ammonium; salts with organic bases such as triethylamine, tributylamine, pyridine and hydrazine. The metal salt of triflumizole can be used as a supply source of the metal cation and triflumizole that constitute the organometallic complex of the present invention.

[0021] In the organometallic complex of the present invention, triflumizole derived from triflumizole and / or a salt thereof is presumed to be contained as a ligand in the organometallic complex.

[0022] The organic acid is an organic compound that exhibits acidity. Examples of organic acids include carboxylic acids, sulfonic acids, dithiocarboxylic acids, compounds having an enol group, compounds having a hydroxy group, and compounds having a hydrothio group. Among these, preferred examples include acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid. These can be used alone or in combination of two or more. Of these, adipic acid, maleic acid, and 2,6-pyridinedicarboxylic acid are more preferred.

[0023] The organic acid salt is not particularly limited as long as it is agriculturally and horticulturally acceptable, and examples thereof include salts with alkali metals such as lithium, sodium, and potassium; salts with alkaline earth metals such as calcium and magnesium; salts with other metals; ammonium; and salts with organic bases such as triethylamine, tributylamine, pyridine, and hydrazine. An organic acid metal salt, which is one type of organic acid salt, can be used as a supply source of the metal cation and organic acid anion that constitute the organometallic complex of the present invention.

[0024] The metal element of the metal cation is preferably at least one metal element selected from the group consisting of elements of Groups 2 to 13 of the periodic table, and among these, a divalent or trivalent metal element is more preferred. Examples of divalent metal elements include zinc, copper, magnesium, calcium, nickel, cobalt, iron, and manganese. Examples of trivalent metal elements include iron, copper, and aluminum. Zinc, copper, magnesium, calcium, nickel, cobalt, iron, and manganese are particularly preferred.

[0025] The metal compound is not particularly limited as long as it can provide a metal cation as the central metal of the complex. Examples of the metal compound used in the present invention include zinc compounds, such as zinc acetylacetonate, zinc malonate, zinc succinate, zinc glutarate, zinc adipate, zinc maleate, zinc benzoate, zinc phthalate, zinc terephthalate, zinc 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt, zinc 2,6-pyridinedicarboxylate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, and zinc N-ethyl-N-phenyldithiocarbamate; and inorganic zinc compounds, such as zinc chloride, zinc nitrate, zinc carbonate, zinc oxide, and zinc hydroxide. Of these, organic acid zinc salts are preferred. Examples of other metal elements include the same compounds as those for zinc element.

[0026] In producing the organometallic complex of the present invention, the molar ratio during mixing is preferably 0.5 to 2 moles, more preferably 0.8 to 1.25 moles, and even more preferably 0.9 to 1.1 moles of metal cation derived from the metal compound relative to 1 mole of triflumizole derived from triflumizole and / or a salt thereof, and preferably 0.25 to 4 moles, more preferably 1.5 to 2.5 moles, and even more preferably 1.8 to 2.2 moles of organic acid anion derived from the organic acid and / or organic acid salt. Note that since a divalent organic acid has two organic acid anions per molecule, the molar ratio during mixing is half of the above number of moles of divalent organic acid relative to 1 mole of triflumizole derived from triflumizole and / or a salt thereof, i.e., preferably 0.125 to 2 moles, more preferably 0.75 to 1.25 moles.

[0027] The organometallic complex of the present invention contains 1 to 4 moles of triflumizole and 1 mole of an organic acid anion (—C(═O)O － , -C(=S)S － , -S(=O) ２ O － , -C=C-O －In the organometallic complex of the present invention, it is presumed that the nitrogen atom at the 3-position in the 1H-imidazol-1-yl group of triflumizole is coordinately bonded to the metal cation. In addition, in the organometallic complex of the present invention, the organic acid anion is a carboxylate (-C(=O)O － ), dithiocarboxylate (-C(=S)S － ), sulfonate (-S(=O) ２ O － ), enolate (-C=C-O － It is presumed that oxygen or sulfur anions in organic acid anions such as thiophene, etc., are bonded to the metal cations.

[0028] In producing the organometallic complex of the present invention, a solvent consisting of only an organic solvent, a solvent consisting of an organic solvent and water, a solvent consisting of a surfactant and water, or a solvent consisting of an organic solvent, a surfactant, and water can be used. Examples of organic solvents include protic polar organic solvents such as methanol, ethanol, isopropanol, n-butanol, and nitromethane; aprotic polar organic solvents such as acetone, anone, N-methylpyrrolidone, dichloromethane, tetrahydrofuran, ethyl acetate, dimethyl sulfoxide, dimethylformamide, acetonitrile, propylene carbonate, and triethylamine; and nonpolar organic solvents such as toluene, benzene, hexane, 1,4-dioxane, chloroform, and diethyl ether. Among these organic solvents, polar organic solvents are preferred.

[0029] The surfactant that can be used in the solvent may be any of the following: anionic surfactants such as carboxylates, sulfonates (LAS, AOS, MES, sulfosuccinates, etc.), and sulfate ester salts (AS, AES, etc.); cationic surfactants such as amine salts and quaternary ammonium salts; nonionic surfactants such as esters (glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, etc.), ethers (polyoxyethylene (or POE) alkyl ethers, polyoxyethylene (or POE) alkylphenyl ethers, etc.), and ester ethers; and amphoteric surfactants such as amino acid types and betaine types.

[0030] The mixing in the production of the organometallic complex of the present invention can be carried out by a known mixing means. Examples of the mixing means include an agitator, homogenizer, ultrasonic grinder, line mixer, bead mill, ball mill, line mill, etc. The temperature of the mixture during mixing is not particularly limited, but is preferably 5 to 50°C.

[0031] The composition of the present invention contains triflumizole, an organometallic complex composed of a metal cation and an organic acid anion, and optionally water. The composition of the present invention can be used as an agricultural and horticultural fungicide.

[0032] The agricultural and horticultural fungicide of the present invention contains an organometallic complex consisting of triflumizole, a metal cation, and an organic acid anion as an active ingredient (hereinafter referred to as active ingredient (I)). The amount of active ingredient (I) contained in the agricultural and horticultural fungicide of the present invention is not particularly limited as long as it exhibits a fungicidal effect.

[0033] The agricultural and horticultural fungicide of the present invention can be used to control plant diseases caused by a wide variety of filamentous fungi, for example, fungi belonging to the phylum Oomycetes, Ascomycetes, Deuteromycetes, Basidiomycetes, and Zygomycetes.

[0034] Examples of plant diseases (pathogens) that can be controlled are shown below. Sugar beet: Cercospora beticola, Aphanomyces cochlioides, Root rot (Thanatephorus cucumeris), Leaf rot (Thananatephorus cucumeris), Rust (Uromyces betae), Powdery mildew (Oidium sp.), Spot disease (Ramularia beticola), Seedling damping off (Aphanomyces cochlioides, Pythium Groundnut: Mycosphaerella arachidis, Ascochyta sp., Puccinia arachidis, Pythium debaryanum, Alternaria alternata, Sclerotium rolfsii, Mycosphaerella berkeleyi, Calonectria ilicicola) etc. Cucumber: Powdery mildew (Sphaerotheca fuliginea), downy mildew (Pseudoperonospora cubensis), vine blight (Mycosphaerella melonis), vine splitting (Fusarium oxysporum), sclerotinia sclerotiorum, gray mold (Botrytis cinerea), anthracnose (Colletotrichum orbiculare), black spot (Cladosporium cucumerinum), brown spot (Corynespora cassiicola), seedling damping-off (Pythium debaryanum, Rhizoctonia solani Kuhn), Phomopsis root rot (Phomopsis sp.), bacterial spot (Pseudomonas syringae pv. Lachrymans), etc. Tomato: Gray mold (Botrytis cinerea), leaf mold (Cladosporium fulvum), late blight (Phytophthora infestans), Verticillium albo-atrum, Verticillium dahliae, powdery mildew (Oidiumneolycopersici), ring blight (Alternaria solani), leaf mold (Pseudocercospora fuligena), bacterial wilt (Ralstonia solanacearum), sclerotinia sclerotiorum, etc. Eggplant: Gray mold (Botrytis cinerea), black blight (Corynespora melongenae), powdery mildew (Erysiphe cichoracearum), leaf mold (Mycovellosiella nattrassii), sclerotinia sclerotiorum, verticillium wilt (Verticillium dahliae), brown spot (Phomopsis vexans), etc. Pepper: Phytophthora capsici, gray mold (Botrytis cinerea), sclerotinia sclerotiorum, anthracnose (Colletotrichum aenigma, Colletotrichum capsici, Colletotrichum fructicola, Colletotrichum jiangxiense), powdery mildew (Leveillula taurica), etc. Strawberry: Gray mold (Botrytis cinerea), powdery mildew (Sphaerotheca humuli), anthracnose (Colletotrichum acutatum, Colletotrichum fragariae), late blight (Phytophthora cactorum), soft rot (Rhizopus stolonifer), chlorosis (Fusarium oxysporum), wilt (Verticillium dahliae), sclerotinia sclerotiorum, etc. Onion: Gray rot (Botrytis allii), gray mold (Botrytis cinerea), white spotted leaf blight (Botrytis squamosa), downy mildew (Peronospora destructor), white late blight (Phytophthora porri), Ciborinia allii, Botrytis squamosa, Fusarium dry rotoxysporum), red root rot (Pyrenochaeta terrestris), black rot sclerotium (Sclerotium cepivorum), rust (Puccinia allii), white silk rot (Sclerotium rolfsii), etc. Allium: soft rot (Pectobacterium carotovorum), downy mildew (Peronospora destructor), leaf blight (Pleospora) cabbage: clubroot (Plasmodiophora brassicae), soft rot (Erwinia), etc. carotovora), black rot (Xanthomonas campesrtis pv. campestris), black spot bacterial disease (Pseudomonas syringae) pv. maculicola, P. s. pv. alisalensis), downy mildew (Peronospora parasitica), sclerotinia sclerotiorum, sooty mildew (Alternaria brassicicola), gray mold (Botrytis cinerea), root rot (Phoma lingam), Pythium rot (Pythium aphanidermatum, Pythium ultimum), white rust (Albugo macrospora), etc. Lettuce: rot (Pseudomonas cichorii, Pseudomonas marginalis), soft rot (Pectobacterium carotovorum), downy mildew (Bremia lactucae), gray mold (Botrytis cinerea), sclerotinia sclerotiorum, big-vein disease (Mirafiori lettuce big-vein ophiovirus), root rot (Fusarium oxysporum), bottom blight (Rhizoctonia solani), powdery mildew (Golovinomyces orontii), etc.Green beans: Sclerotinia sclerotiorum, Botrytis cinerea, Colletotrichum lindemuthianum, Phaeoisariopsis griseola, etc. Peas: Mycosphaerella blight, Botrytis cinerea, Sclerotinia sclerotiorum, Powdery mildew, Erysiphe pisi, etc.

[0035] Apple: Powdery mildew (Podosphaera leucotricha), black spot (Venturia inaequalis), monilinia (Monilinia mali), black spot (Mycosphaerella pomi), canker (Valsa mali), leaf spot (Alternaria mali), red spot (Gymnosporangium yamadae), ring spot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), sooty spot (Zygophiala jamaicensis), sooty spot (Gloeodes pomigena), purple root rot (Helicobasidium mompa), white root rot (Rosellinia necatrix), gray mold (Botrytis cinerea), fire blight (Erwinia amylovora), silver leaf (Chondrostereum) purpureum), crown gall (Rhizobium radiobacter, Rhizobium rhizogenes), etc. Plum: Black spot (Cladosporium carpophilum), gray mold (Botrytis cinerea), brown rot (Monilinia mumecola), sooty spot (Peltaster sp.), fruit blister (Taphrina pruni), brown hole (Phloeosporella padi), etc. Persimmon: Powdery mildew (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), angular leaf spot (Cercospora kaki), circular leaf spot (Mycosphaerella nawae), gray mold (Botrytis cinerea), sooty spot (Zygophiala jamaicensis), etc. Peach: Brown rot (Monilinia fructicola, Monilinia fructigena), black spot (Cladosporium carpophilum), Phomopsis sp., Xanthomonas campestris pv.Plum: leaf curl (Taphrina pruni), leaf blister (Taphrina deformans), anthracnose (Colletotrichum gloeosporioides), brown leaf spot (Phloeosporella padi), wood ear (Coriolus versicolor), etc. Almond: gray mold (Monilinia laxa), leaf blotch (Stigmina carpophila), black leaf spot (Cladosporium carpophilum), leaf swelling disease (Polystigma rubrum), Alternaria leaf spot (Alternaria alternata), anthracnose (Colletotrichum gloeospoides), etc. Peach: gray mold (Monilinia fructicola), anthracnose (Colletotrichum acutatum), black spot (Alternaria sp.), Young fruit sclerotinia (Monilinia kusanoi), Brown hole (Mycosphaerella cerasella), Powdery mildew (Podosphaera tridactyla), etc. Grapes: Gray mold (Botrytis cinerea), Powdery mildew (Uncinula necator), Late rot (Glomerella cingulata, Colletotrichum acutatum), Downy mildew (Plasmopara viticola), Black rot (Elsinoe ampelina), Brown spot (Pseudocercospora vitis), Black rot (Guignardia bidwellii), White rot (Coniella castaneicola), Rust (Phakopsora ampelopsidis), White cotton snow (causative agent unidentified), Crown gall (Rhizobium radiobacter, Rhizobium vitis), etc. Pears: Black spot (Venturia nashicola), Red spot (Gymnosporangium asiaticum), black spot (Alternaria kikuchiana), ring spot (Botryosphaeria berengeriana), powdery mildew (Phyllactinia mali), canker (Phomopsis fukushii), brown spot (Stempphylium vesicarium), anthracnose (Glomerella cingulata), etc. Tea: ring spot (Pestalotiopsis longiseta, P. theae), anthracnose (Colletotrichum theae-sinensis), net blight (Exobasidium reticulatum), red burn (Pseudomonas syringae), blight (Exobasidium vexans), etc. Citrus: scab (Elsinoe fawcettii), blue mold (Penicillium italicum), green mold (Penicillium digitatum), gray mold (Botrytis cinerea), black spot (Diaporthe citri), canker (Xanthomonas campestris pv. Citri), powdery mildew (Oidium sp.), late blight (Phytophthora citrophthora), anthracnose (Colletotrichum fioriniae), etc. Kiwifruit: blossom rot (Pseudomonas marginalis, Pseudomonas syringae, Pseudomonas viridiflava), canker (Pseudomonas syringae), gray mold (Botrytis cinerea), fruit soft rot (Botryosphaeria dothidea, Diaporthe sp., Lasiodiplodia theobromae), sooty spot (Pseudocercospora actinidiae), etc. Olive: anthracnose (Colletotrichum acutatum, Colletotrichum gloeosporioides), peacock spot (Spilocaea oleaginea), etc. Chestnut: anthracnose (Colletotrichum gloeosporioides), etc.

[0036] Wheat: powdery mildew (Blumeria graminis f.sp. tritici), head blight (Gibberella zeae, Fusarium avenaceum, Fusarium culmorum, Fusarium crookwellense, Microdochium nivale), brown rust (Puccinia recondita), yellow rust (Puccinia striiformis), brown snow blight (Pythium iwayamai), red snow blight (Monographella nivalis), eyespot (Pseudocercosporella herpotrichoides), leaf blotch (Septoria tritici), glume blotch (Leptosphaeria nodorum), pink snow mold (Typhula incarnata), gray snow mold (Myriosclerotinia borealis), take-all (Gaeumannomyces graminis), ergot (Claviceps purpurea), common bunt (Tilletia caries), loose smut (Ustilago nuda), blast (Pyricularia grisea), damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Barley: leaf stripe (Pyrenophora graminea), net blotch (Pyrenophora teres), scald (Rhynchosporium secalis), loose smut (Ustilago tritici, U. nuda), damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Rice: blast (Pyricularia oryzae), sheath blight (Rhizoctonia solani), bakanae disease (Gibberella fujikuroi), sesame leaf blight (Cochliobolusmiyabeanus), seedling damping-off (Pythium graminicola), white leaf blight (Xanthomonas oryzae), bacterial seedling damping-off (Burkholderia plantarii), brown stripe (Acidovorax avenae), bacterial grain rot (Burkholderia glumae), streak leaf blight (Cercospora oryzae), rice smut (Ustilaginoidea virens), brown rice (Alternaria alternata, Curvularia intermedia), black-bellied rice (Alternaria padwickii), pink rice (Epicoccum purpurascens), etc. Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum), late blight (Phytophthora nicotianae), etc. Tulip: Gray mold (Botrytis cinerea), brown spot (Botrytis tulipae), leaf rot (Rhizoctonia solani), bulb rot (Fusarium oxysporum), skin rot (Rhizoctonia solani), etc. Roses: black spot (Diplocarpon rosae), powdery mildew (Erysiphe simulans, Podosphaera pannosa), gray mold (Botrytis cinerea), etc. Chrysanthemums: gray mold (Botrytis cinerea), white rust (Puccinia horiana), downy mildew (Paraperonospora minor, Peronospora danica), Pythium damping-off (Pythium aphanidermatum, Pythium dissotocum, Pythium helicoides, Pythium oedochilum, Pythium sylvaticum), damping-off (Rhizoctonia solani), Fusarium damping-off (Fusarium solani), etc. Gerberas: gray mold (Botrytis cinerea), powdery mildew (Podosphaera xanthii), etc. Lily: Leaf blight (Botrytis elliptica, Pestalotiopsissp.), Gray mold (Botrytis cinerea), etc. Sunflower: Downy mildew (Plasmopara halstedii), Sclerotinia sclerotiorum, Gray mold (Botrytis cinerea), etc. Bentgrass: Snow mold (Sclerotinia borealis), Large patch (Rhizoctonia solani), Brown patch (Rhizoctonia solani), Dollar spot (Sclerotinia homoeocarpa), Blast (Pyricularia sp.), Blight (Pythium aphanidermatum), Anthracnose (Colletotrichum graminicola), etc. Orchardgrass: Powdery mildew (Erysiphe graminis), etc. Soybean: Purple spot (Cercospora kikuchii), Downy mildew (Peronospora manshurica), Stem rot (Phytophthora sojae), Rust (Phakopsora pachyrhizi), Sclerotinia sclerotiorum, Anthracnose (Colletotrichum truncatum), Gray mold (Botrytis cinerea), Black rot (Elsinoe glycines), Black spot (Diaporthe phaseolorum var. sojae), Damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), Seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Potato: Late blight (Phytophthora infestans), Summer blight (Alternaria solani), Black spot (Thanatephorus cucumeris), Verticillium wilt (Verticillium albo-atrum, V. dahliae, V. nigrescens), Black leg (Pectobacterium atrosepticum), soft rot (Pectobacterium carotovorum), gray mold (Botrytis cinerea), common scab (Streptomycesspp.), Sclerotinia sclerotiorum, etc. Yam: Leaf blight (Cylindrosporium dioscoreae), Anthracnose (Colletotrichum gloeosporioides), Blue mold (Penicillium sclerotigenum), etc. Sweet potato: Purple root rot (Helicobasidium mompa), Fusarium oxysporum, etc. Taro: Late blight (Phytophthora colocasiae), Stem rot (Rhizoctonia solani), etc. Ginger: Rhizome rot (Pythium ultimum, Pythium myriotylum), White spot (Phyllosticta zingiberis), etc. Banana: Panama disease (Fusarium oxysporum), Sigatoka disease (Mycosphaerella fijiensis, M. musicola), etc. Mango: Anthracnose (Colletotrichum aenigma), canker (Xanthomonas campestris), stem rot (Diaporthe pseudophoenicicola, Lasiodiplodia theobromae, Lasiodiplodia spp., Neofusicoccum parvum, Neofusicoccum sp.), gray mold (Botrytis cinerea), etc. Rapeseed: Sclerotinia sclerotiorum, root rot (Phoma lingam), black spot (Alternaria brassicae), powdery mildew (Erysiphe cruciferarum, Erysiphe cichoracearum, Oidium matthiolae), downy mildew (Peronospora parasitica), etc. Coffee: Rust (Hemileia vastatrix), anthracnose (Colletotrichum coffeanum), brown eye (Cercospora coffeicola), etc. Sugarcane: Brown rust (Puccinia melanocephala) etc. Corn: Hail leaf spot (Gloeocercospora sorghi), rust (Pucciniasorghi), southern rust (Puccinia polysora), ear smut (Ustilago maydis), southern leaf blight (Cochliobolus heterostrophus), sooty blight (Setosphaeria turcica), damping off (Pythium spp., Fusarium spp., Rhizoctonia spp.), seedling blight (Pythium spp., Fusarium spp., Rhizoctonia spp.), etc. Cotton: seedling damping-off (Pythium sp.), rust (Phakopsora gossypii), white mold (Mycosphaerella areola), anthracnose (Glomerella gossypii), etc. Hops: downy mildew (Pseudoperonospora humuli), powdery mildew (Oidium sp., Podosphaera macularis), gray mold (Botrytis cinerea), etc.

[0037] The agricultural and horticultural fungicide of the present invention is preferably used on plants such as grains, vegetables, root vegetables, potatoes, fruit trees, trees such as tea, coffee and cacao, pasture grasses, turf grasses, and cotton.

[0038] The agricultural and horticultural fungicide of the present invention can be applied to various parts of plants, such as leaves, stems, stalks, flowers, buds, fruits, seeds, sprouts, roots, tubers, tuberous roots, shoots, cuttings, etc. It can also be applied to improved varieties and varieties of these plants, cultivated varieties, mutants, hybrids, and genetically modified organisms (GMOs).

[0039] The agricultural and horticultural fungicide of the present invention can be used for seed treatment, foliage spray, soil application, water surface application, etc., which are carried out to control various diseases that occur in agricultural and horticultural crops including flowers, turf, and pasture grass.

[0040] The agricultural and horticultural fungicide of the present invention may contain other components in addition to the active ingredient (I). Examples of such other components include known carriers used for formulation. Examples of such other components include conventionally known fungicides, insecticides / miticides, nematicides, soil pesticides, plant regulators, synergists, fertilizers, soil conditioners, and animal feed (hereinafter sometimes referred to as active ingredient (II)). The agricultural and horticultural fungicide of the present invention may exhibit a synergistic effect by containing the active ingredients (I) and (II). The agricultural and horticultural fungicide of the present invention may also be mixed or used in combination with an agricultural or horticultural agent containing the active ingredient (II). Mixing or use in combination may produce a synergistic effect.

[0041] Specific examples of fungicides as the active ingredient (II) are shown below. (1) Nucleic acid biosynthesis inhibitors: (a) RNA polymerase I inhibitors: benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M, oxadixyl, clozylacon, ofrace; (b) Adenosine deaminase inhibitors: bupirimate, dimethirimol, ethirimol; (c) DNA / RNA synthesis inhibitors: hymexazole, octhilinone; (d) DNA topoisomerase II inhibitors: oxolinic acid;

[0042] (2) Mitotic inhibitors and cell division inhibitors: (a) β-tubulin polymerization inhibitors: benomyl, carbendazim, chlorphenazole, fuberidazole, thiabendazole, thiophanate, thiophanate methyl, diethofencarb, zoxamide, ethaboxam; (b) cell division inhibitors: pencycuron; (c) spectrin-like protein delocalization inhibitors: fluopicolide, fluopimomide;

[0043] (3) Respiratory inhibitors: (a) Complex I-NADH oxidoreductase inhibitors: diflumetrim, tolfenpyrad; (b) Complex II-succinate dehydrogenase inhibitors: benodanil, flutolanil, mepronil, isofetamide, fluopyram, fenfuram, flumecyclox, carboxin, oxycarboxin, thifluzamide, benzovindiflupyr, bixafen, fluxapyroxad, furametpyr, isopyrazam, penflufen, penthiopyrad, sedaxane, boscalid, pydiflumetofen, isoflucipram, pyraziflumid, inpirfluxam; (c) Complex III - ubiquinol oxidase Qo inhibitors: azoxystrobin, cumoxystrobin, methoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, phenaminestrobin, metominostrobin, orysastrobin, famoxadone, fluoxastrobin, fenamidone, pyribencarb, methyltetraprole, mandestrobin; (d) Complex III - ubiquinol reductase Qi inhibitors: cyazofamid, amisulbrom, fenpicoxamide; (e) oxidative phosphorylation uncouplers: binapacryl, meptyldinocap, dinocap, fluazinam, ferimzone; (f) Oxidative phosphorylation inhibitors (inhibitors of ATP synthase): fentin acetate, fentin chloride, fentin hydroxide; (g) ATP production inhibitors: silthiofam; (h) Complex III: Qx (unknown) inhibitor of cytochrome bc1 (ubiquinone reductase): ametoctradine;

[0044] (4) Amino acid and protein synthesis inhibitors: (a) methionine biosynthesis inhibitors: andoprim, cyprodinil, mepanipyrim, pyrimethanil; (b) protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride, streptomycin, oxytetracycline;

[0045] (5) Signal transduction inhibitors: (a) Signal transduction inhibitors: quinoxyfen, proquinazid; (b) MAP / histidine kinase inhibitors in osmotic signal transduction: fenpiclonil, fludioxonil, chlozolinate, iprodione, procymidone, vinclozolin;

[0046] (6) Lipid and cell membrane synthesis inhibitors: (a) phospholipid biosynthesis, methyltransferase inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; (b) lipid peroxidants: biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl, etridiazole; (c) agents acting on cell membranes: iodocarb, propamocarb, propamocarb hydrochloride, propamocarb focetylate, prothiocarb; (d) microorganisms disrupting pathogenic cell membranes: Bacillus subtilis, Bacillus subtilis QST713 strain, Bacillus subtilis FZB24 strain, Bacillus subtilis MBI600 strain, Bacillus subtilis D747 strain, Bacillus amyloliquefaciens; (e) agents disrupting cell membranes: tea tree extract;

[0047] (7) Cell membrane sterol biosynthesis inhibitors: (a) C14 demethylation inhibitors in sterol biosynthesis: triforine, pyrifenox, pyrisoxazole, fenarimol, flurprimidol, nuarimol, imazalil, imazalil sulfate, oxpoconazole, oxpoconazole fumarate, pefurazoate, prochloraz, triflumizole, biniconazole, azaconazole, bitertanol, bromuconazole, cyproconazole, diclobutrazol, difenoconazole, diniconazole, diniconazole-M, epoxi Siconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, fluconazole, fluconazole-cis, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, fluquinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, prothioconazole, voriconazole, mefentrifluconazole; (b) Inhibitors of Δ14 reductase and Δ8→Δ7-isomerase in sterol biosynthesis: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine; (c) Inhibitors of 3-ketoreductase in C4 demethylation of the sterol biosynthesis pathway: fenhexamid, fenpyrazamine; (d) Inhibitors of squalene epoxidase in the sterol biosynthesis pathway: pyributicarb, naftifine, terbinafine;

[0048] (8) Cell wall synthesis inhibitors: (a) trehalase inhibitors: validamycin; (b) chitin synthase inhibitors: polyoxin, polyoxolim; (c) cellulose synthase inhibitors: dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb isopropyl, iprovalicarb, valifenalate, mandipropamide;

[0049] (9) Melanin biosynthesis inhibitors (a) Reductase inhibitors of melanin biosynthesis: fthalide, pyroquilon, tricyclazole; (b) Dehydratase inhibitors of melanin biosynthesis: carpropamid, diclocymet, fenoxanil; (c) Polyketide synthesis inhibitors of melanin biosynthesis: tolprocarb;

[0050] (10) Resistance inducers of host plants: (a) Agents acting on the salicylic acid synthesis pathway: acibenzolar-S-methyl; (b) Others: probenazole, tiadinil, isotianil, diclobenthiazox, ipfentrifluconazole, laminarin, giant knotweed extract, phosphorous acid, phosphites;

[0051] (11) Agents of unknown activity: cymoxanil, fosetyl aluminum, phosphoric acid, phosphate salts, tecloftalam, triazoxide, flusulfamide, diclomedine, metasulfocarb, cyflufenamid, metrafenone, pyriophenone, dodine, dodine free base, fluthianil;

[0052] (12) Agents with multiple action sites: copper (copper salts), Bordeaux mixture, copper hydroxide, copper naphthalate, copper oxide, copper oxychloride, copper sulfate, sulfur, sulfur products, calcium polysulfide, ferbam, mancozeb, maneb, mancopper, metiram, polycarbamate, propineb, thiram, zineb, ziram, captan, captafol, folpet, chlorothalonil, dichlofluanid, tolylfluanid, guazatine, guazatine triacetate (also known as iminoctadine triacetate), iminoctadine tribesylate, anilazine, dithianone, chinomethionate, fluorimide;

[0053] (13) Other agents: DBEDC, fluorofolpet, guazatine acetate, bis(8-quinolinolato)copper(II), propamidine, chloropicrin, cyproflam, Agrobacterium, bethoxadin, diphenylamine, methylisothianate (MITC), mildeomycin, capsaicin, kufuraneb, cyprosulfamide, dazomet, debacarb, dichlorophen, difenzoquat, difenzoquat methylsulfonate, flumetober, fosetyl calcium, fosetyl sodium, irumamycin, natamycin, nitrotar isopropyl, oxamocarb, pyrrolnitrin, tebufloquin, tolnifanide, zaliramide, algophase, amical Thiazole, oxathiapiprolin, fluoxapiprolin, metiram zinc, benthiazole, trichlamide, uniconazole, oxyfenthiin, picarbutrazox, diclobenthiazox, quinofumelin, thiuram, ambam, Agrobacterium radiobacter, Coniothyrium minitans, Pseudomonas fluorescens, Pseudomonas rhodesia, Talaromyces flavus, Trichoderma atroviride, non-pathogenic Erwinia carotovora, Bacillus simplex, Variovorax paradoxus, Lactobacillus plantarum, florylpicoxamide, pyrapropoin, fluindapyr, aminopyrifen, pyridaclomethyl, ipflufenoquin, dipimethitron;

[0054] Specific examples of insecticides, acaricides, nematicides, soil pesticides, anthelmintics, etc. as the active ingredient (II) are shown below.

[0055] (1) Acetylcholinesterase (AChE) inhibitors (a) Carbamate acetylcholinesterase (AChE) inhibitors: alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC, xylylcarb, fenothiocarb, MIPC, MPMC, MTMC, aldoxycarb, alixycarb, aminocarb, bufencarb, cloethocarb, metam sodium, promecarb;(b) Organophosphate acetylcholinesterase (AChE) inhibitors: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fenflur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyaphos, isofenphos, isocarbophos, isopropyl = O- (methoxyaminothiophosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, para Thionemethyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, trichlorfon, vamidothion, bromophos-ethyl, BRP, carbophenothion, cyanofenphos, CYAP, demeton-S-methylsulfone, dialifos, diclofenthion, dioxabenzophos, etrimphos, fensulfothion, flupyrazophos, fonofos, formothion, fosmetilan, isazophos, iodofenphos, methacrifos, pirimiphos-ethyl, phosphocarb, propafos, protoate, sulprofos;

[0056] (2) GABA-activated chloride ion (chloride ion) channel blockers: acetoprole, chlordane, endosulfan, ethiprole, fipronil, pyrafluprole, pyriprole, camphechlor, heptachlor, dienochlor, and flufiprole;

[0057] (3) Sodium channel modulators (a) Pyrethroid sodium channel modulators: acrinathrin, allethrin, d-cis-trans-allethrin, d-trans-allethrin, bifenthrin, bioallethrin, bioallethrin-S-cyclopentenyl-isomer, bioresmethrin, cycloprothrin, cyfluthrin, β-cyfluthrin, cyhalothrin, λ-cyhalothrin, γ-cyhalothrin, cypermethrin, α-cypermethrin, β-cypermethrin, θ-cypermethrin Permethrin, ζ-cypermethrin, cyphenothrin [(1R)-trans isomer], deltamethrin, empenthrin [(EZ)-(1R)-isomer], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, τ-fluvalinate, halfenprox, imiprothrin, kadesrin, permethrin, phenothrin thrin [(1R)-trans isomer], prallethrin, pyrethrum, pyrethrin, resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomer], tralomethrin, transfluthrin, allethrin, pyrethrin I, pyrethrin II, profluthrin, dimefluthrin, bioethanomethrin, biopermethrin, transpermethrin, fenfluthrin, fenpyrithrin, flubrocythrinate, flufenprox, metofluthrin, protrifenbut, pyresmethrin, telallethrin, κ-bifenthrin, chloroprallethrin, heptafluthrin, meperfluthrin, ε-metofluthrin, monfluorothrin, ε-monfluorothrin, κ-tefluthrin, tetramethylfluthrin, bioethanomethrin; (b) Sodium channel modulators (DDTs): DDT, methoxychlor;

[0058] (4) Nicotinic acetylcholine receptor (nAChR) competitive modulators: acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, nithiazine, thiacloprid, thiamethoxam, nicotine, sulfoxaflor, flupyradifurone, triflumezopyrim, dichloromezothiazol, flupirimine; (5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators: spinetoram, spinosad; (6) Glutamate-activated chloride ion (chloride ion) channel (GluCl) allosteric modulators: abamectin, emamectin, emamectin benzoate, lepimectin, milbemectin, ivermectin, selamectin, doramectin, eprinomectin, ivermectin, moxidectin, selamectin, milbemycin, milbemycin oxime, nemadectin;

[0059] (7) Juvenile hormone analogues: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen, diofenolan, epofenonane, triprene; (8) Other non-specific (multi-site) inhibitors: methyl bromide, alkyl halides, chloropicrin, sodium aluminum fluoride, sulfuryl fluoride, borax, boric acid, disodium octaborate, sodium borate, sodium metaborate, tartar emetic, dazomet, metam, metam potassium salt, metam sodium salt; (9) Chordotonal organ TRPV channel modulators: flonicamid, pymetrozine, pyrifluquinazone, afidopiropen; (10) Mite growth inhibitors: clofentezine, diflobidazine, hexythiazox, etoxazole; (11) Microbial-derived insect midgut membrane disruptors: Proteins found in Bacillus thuringiensis subspecies israerenci, Bacillus sphaericus, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis, Bt crops: Cry1Ab, Cry1Ac, Cry1Fa, Cry1A.105, Cry2Ab, Vip3A, mCry3A, Cry3Ab, Cry3Bb, Cry34Ab1 / Cry35Ab1; Bacillus sphaericus;

[0060] (12) Mitochondrial ATP synthase inhibitors: diafenthiuron, azocyclotine, cyhexatin, fenbutatin oxide, propargite, tetradifon; (13) oxidative phosphorylation uncouplers that disrupt the proton gradient: chlorfenapyr, DNOC, sulfuramide, binapacryl, dinobuton, dinocap; (14) nicotinic acetylcholine receptor (nAChR) channel blockers: bensultap, cartap hydrochloride, nereistoxin, thiocyclam, thiosultap-sodium salt; (15) chitin biosynthesis inhibitors, type 0: bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, triflumuron, buprofezin, fluazuron; (16) chitin biosynthesis inhibitors, type 1: (17) Molting inhibitors: cyromazine; (18) Molting hormone (ecdysone) receptor agonists: chromafenozide, halofenozide, methoxyfenozide, tebufenozide;

[0061] (19) Octopamine receptor agonists: amitraz, demiditraz, chlordimeform; (20) Mitochondrial electron transport chain complex III inhibitors: hydramethylnon, acequinocyl, fluacrypyrim, bifenazate; (21) Mitochondrial electron transport chain complex I inhibitors (METI): fenazaquin, fenpiroximate, pyridaben, pyrimidifen, tebufenpyrad, tolfenpyrad, rotenone; (22) Voltage-dependent sodium channel blockers: indoxacarb, metaflumizone; (23) Acetyl-CoA carboxylase inhibitors: spirodiclofen, spiromesifen, spirotetramat, spiropidione; (24) Mitochondrial electron transport chain complex IV inhibitors: aluminum phosphide, calcium phosphide, zinc phosphide, phosphine, cyanide, calcium cyanide, sodium cyanide, potassium cyanide; (25) Mitochondrial electron transport chain complex II inhibitors: Cyenopyrafen, cyflumetofen, piflubumid;

[0062] (28) Ryanodine receptor modulators: chlorantraniliprole, cyantraniliprole, cyclaniliprole, flubendiamide, cyhalodiamide, tetrachlorantraniliprole, tetraniliprole; (29) Chordotonal organ modulators, target site unspecified: flonicamide; (30) GABA-gated chloride ion (chloride ion) channel allosteric modulators: broflanilide, fluxamethamide, isocycloceram, afoxolaner, fluralaner, lotineral, sarolaner; (31) Other insecticides, acaricides: Azadirachtin, benzoximate, bifenazate, bromopropylate, chinomethionate, cryolite, dicofol, lime sulfur mixture, mancozeb, pyridalyl, benclothiaz, sulfur, amidoflumet, 1,3-dichloropropene, DCIP, phenisobromorate, benzomate, metaldehyde, chlorbenzilate, clothiazoben, dicyclanil, fenoxacrim, fentrifanil, flubenzimine, fluphenazine, gossiplura, japonirua, methoxadiazone, petroleum oil, potassium oleate, tetrasulfur, triarane, afidopiropen, flufifol, fluensulfone, meperfluthrin, tetramethylfluthrin, tralopyril, dimefluthrin, methylneodecane Amide, fluralaner, afoxolaner, fluxametamide, 5-[5-(3,5-dichlorophenyl)-5-trifluoromethyl-4,5-dihydroisoxazol-3-yl]-2-(1H-1,2,4-triazol-1-yl)benzonitrile (CAS: 943137-49-3), broflanilide, other metadiamides, Steinernema carpocapsae, Steinernema glaceri, Pasteuria penetrans, Pecilomyces tenuipes, Pecilomyces fumosoroseus, Beauveria bassiana, Beauveria brongniartii, Metarhizium anisopliae, Verticillium lecanii, acinonapyr, benzpyrimoxane, flometoquin, fluhexafon, oxazosulfil, cyclopyrazoflor.

[0063] (32) Anthelmintics: (a) Benzimidazoles: fenbendazole, albendazole, triclabendazole, oxibendazole, mebendazole, oxfendazole, perbendazole, flubendazole, febantel, netobimin, thiophanate, thiabendazole, cambandazole; (b) Salicylanilides: closantel, oxyclozanide, rafoxanide, niclosamide; (c) Substituted phenols: nitroxynil, nitroscanate; (d) Pyrimidines: pyrantel, morantel; (e) Imidazothiazoles: levamisole, tetramisole; (f) Tetrahydropyrimidines: praziquantel, epsiprantel; (g) Other anthelmintics: Cyclodien, riania, clorsulon, metronidazole, demiditraz, piperazine, diethylcarbamazine, dichlorophen, monepantel, tribendimidine, amidantel, thiacetarsamide, melarsomine, arsenamide.

[0064] Specific examples of plant regulators as the active ingredient (II) are shown below: abscisic acid, kinetin, benzylaminopurine, 1,3-diphenylurea, forchlorfenuron, thidiazuron, chlorfenuron, dihydrozeatin, gibberellin A, gibberellin A4, gibberellin A7, gibberellin A3, 1-methylcyclopropane, N-acetylaminoethoxyvinylglycine (also known as abiglycine), aminooxyacetic acid, silver nitrate, cobalt chloride, IAA, 4-CPA, cloprop, 2,4-D, MCPB, indole-3-butyric acid, dichlorprop, phenothionyl ol, 1-naphthylacetamide, ethychlozate, cloxifonac, maleic hydrazide, 2,3,5-triiodobenzoic acid, salicylic acid, methyl salicylate, (-)-jasmonic acid, methyl jasmonate, (+)-strigol, (+)-deoxystrigol, (+)-orobanchol, (+)-sorgolactone, 4-oxo-4-(2-phenylethyl)aminobutyric acid, ethephon, chlormequat, mepiquat chloride, benzyladenine, 5-aminolevulinic acid, daminozide.

[0065] {Formulation} The agricultural and horticultural fungicide of the present invention is not particularly limited by its formulation. For example, it may be in the form of a wettable powder, emulsifiable concentrate, dust, granule, water-soluble powder, suspension, water-dispersible granule, tablet, etc. The method for preparing the formulation is not particularly limited, and a known preparation method can be used depending on the formulation.

[0066] Examples of auxiliary components that may be contained in the composition containing the organometallic complex of the present invention include surfactants, extenders, efficacy enhancing aids, antioxidants, ultraviolet absorbers, stabilizers, and the like.

[0067] Examples of surfactants that can be contained in the composition containing the organometallic complex of the present invention include nonionic surfactants such as polyoxyethylene-added alkyl phenyl ethers, polyoxyethylene-added alkyl ethers, polyoxyethylene-added higher fatty acid esters, polyoxyethylene-added sorbitan higher fatty acid esters, and polyoxyethylene-added tristyryl phenyl ethers; sulfate salts of polyoxyethylene-added alkyl phenyl ethers, alkylbenzene sulfonates, sulfate salts of higher alcohols, alkylnaphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkylnaphthalene sulfonates, and isobutylene-maleic anhydride copolymers.

[0068] Examples of extenders that can be contained in the composition containing the organometallic complex of the present invention include the following. Solvents: water, glycerin, ethylene glycol, propylene glycol, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, alcohol, aliphatic hydrocarbons, aromatic hydrocarbons, etc.; Thickeners, stabilizers, binders: polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyethylene glycol, carboxymethyl cellulose, hydroxypropyl cellulose, gum arabic, xanthan gum, gelatin, casein, pectin, sodium alginate, etc.; Solid carriers: mineral powders such as talc, clay, bentonite, kaolinite clay, montmorillonite, pyroferrite, acid clay, diatomaceous earth, vermiculite, apatite, gypsum, mica, silica sand, calcium carbonate, and pumice powder; synthetic products such as white carbon (amorphous silica) and titanium dioxide; vegetable powders such as crystalline cellulose, starch, wood flour, cork, and coffee husks; polymer compounds such as polyvinyl chloride and petroleum resin; Water-soluble components: Ammonium sulfate, ammonium nitrate, ammonium chloride, potassium phosphate, potassium chloride, urea, sugars; etc.

[0069] Some formulation examples are shown below. Note that the formulations shown below are merely examples and can be modified within the scope of the present invention, and the present invention is not limited by the following formulation examples. Unless otherwise specified, "parts" means "parts by mass."

[0070] (Formulation Example 1: Wettable Powder) 40 parts of the organometallic complex of the present invention, 53 parts of diatomaceous earth, 4 parts of higher alcohol sulfate, and 3 parts of alkylnaphthalene sulfonate are uniformly mixed and then finely pulverized to obtain a wettable powder containing 40% by mass of the active ingredient.

[0071] (Formulation Example 2: Granules) 5 parts of the organometallic complex of the present invention, 40 parts of talc, 38 parts of clay, 10 parts of bentonite, and 7 parts of sodium alkyl sulfate are uniformly mixed, then finely pulverized, and then granulated to particle diameters of 0.5 to 1.0 mm to obtain granules containing 5% by mass of the active ingredient.

[0072] Formulation Example 3: Granules 5 parts of the organometallic complex of the present invention, 73 parts of clay, 20 parts of bentonite, 1 part of dioctyl sulfosuccinate sodium salt, and 1 part of potassium phosphate are uniformly mixed and pulverized, and then water is added thereto and kneaded. The mixture is then granulated and dried to obtain granules containing 5% by mass of the active ingredient.

[0073] (Formulation Example 4: Suspension) 10 parts of the organometallic complex of the present invention, 4 parts of polyoxyethylene alkyl allyl ether, 2 parts of a sodium polycarboxylate, 10 parts of glycerin, 0.2 parts of xanthan gum, and 73.8 parts of water are mixed and wet-pulverized until the particle size becomes 3 microns or less, to obtain a suspension containing 10% by mass of the active ingredient.

[0074] (Formulation Example 5: Water Dispersible Granules) 40 parts of the organometallic complex of the present invention, 36 parts of clay, 10 parts of potassium chloride, 1 part of sodium alkylbenzenesulfonate, 8 parts of sodium ligninsulfonate, and 5 parts of a formaldehyde condensate of sodium alkylbenzenesulfonate are uniformly mixed and finely pulverized. An appropriate amount of water is then added to the mixture, and the mixture is kneaded to form a clay-like substance. The clay-like substance is granulated and then dried to obtain a water dispersible granule containing 40% by mass of the active ingredient.

[0075] Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples. Note that "parts" are values ​​based on mass.

[0076] In this example, the solid product was evaluated by the following method. [Powder X-ray diffraction] A sample was filled into the sample filling section of a silicon non-reflective test plate, and a diffraction chart was obtained by measurement at a scan rate of 24° / min using a powder X-ray diffractometer (D2 PHASER, manufactured by Bruker) equipped with an X-ray source (Cu, 30 kV-10 mA). Figure 1 shows the diffraction chart of triflumizole. In the diffraction chart, the vertical axis represents intensity and the horizontal axis represents diffraction angle.

[0077] Example 1: 1 part of triflumizole, 0.89 parts of zinc benzoate (approximately 1 mole of zinc cations and approximately 2 moles of benzoate anions per mole of triflumizole), 30 parts of dichloromethane, and 20 parts of methanol were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of benzoate anions). Figure 2 shows the diffraction chart of zinc benzoate. Figure 3 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.34°, 9.48°, 10.92°, 11.19°, 14.46°, 15.23°, 16.86°, 18.92°, 19.75°, 19.98°, 23.87°, 24.41°, and 25.84°. The solid product has a different crystal structure from triflumizole and zinc benzoate.

[0078] Example 2 0.50 parts of triflumizole, 0.52 parts of zinc diethyldithiocarbamate (approximately 1 mole of zinc cations and approximately 2 moles of diethyldithiocarbamate anions per mole of triflumizole), and 20 parts of dichloromethane were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of diethyldithiocarbamate anions). Figure 4 shows the diffraction chart of zinc diethyldithiocarbamate. Figure 5 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 9.34°, 12.10°, 13.92°, 14.53°, 15.86°, 16.55°, 17.77°, 19.69°, 21.34°, 23.30°, and 27.91°. The solid product has a different crystal structure from triflumizole and zinc diethyldithiocarbamate.

[0079] Example 3 0.51 parts of triflumizole, 0.66 parts of zinc N-ethyl-N-phenyldithiocarbamate (approximately 1 mole of zinc cations and approximately 2 moles of N-ethyl-N-phenyldithiocarbamate anions per mole of triflumizole), 30 parts of dichloromethane, and 10 parts of methanol were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of N-ethyl-N-phenyldithiocarbamate anions). Figure 6 shows a diffraction chart of zinc N-ethyl-N-phenyldithiocarbamate. Figure 7 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.61°, 6.99°, 12.44°, 14.18°, 14.61°, 17.33°, 18.33°, 20.45°, 21.44°, 21.82°, and 24.56°. The solid product has a different crystal structure from triflumizole and zinc N-ethyl-N-phenyldithiocarbamate.

[0080] Example 4: 0.51 parts of triflumizole, 0.38 parts of zinc acetylacetonate (approximately 1 mole of zinc cations and approximately 2 moles of acetylacetonate anions per mole of triflumizole), and 20 parts of dichloromethane were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting solution using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of acetylacetonate anions). Figure 8 shows the diffraction chart of zinc acetylacetonate. Figure 9 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.64°, 9.36°, 11.93°, 13.95°, 18.01°, 20.22°, 22.79°, 23.62°, 23.47°, and 24.25°. The solid product had a different crystal structure from triflumizole and zinc acetylacetonate.

[0081] Example 5: 1 part triflumizole, 0.6 parts zinc adipate (approximately 1 mole of zinc cations and approximately 1 mole of adipate anions per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.5 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 2 moles of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of adipate anions). Figure 10 shows the diffraction chart of zinc adipate. Figure 11 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.30°, 10.65°, 12.11°, 16.21°, 16.76°, 18.18°, 19.90°, 21.24°, and 21.85°. The solid product had a different crystal structure from triflumizole and zinc adipate.

[0082] Example 6: 1 part triflumizole, 0.6 parts zinc maleate (approximately 1 mole of zinc cations and approximately 1 mole of maleate anions per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.5 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of maleate anions). Figure 12 shows the diffraction chart of zinc maleate. Figure 13 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.30°, 10.10°, 11.78°, 14.04°, 14.52°, 15.37°, 16.72°, 19.33°, 20.78°, 21.77°, 22.92°, and 25.94°. The solid product has a different crystal structure from triflumizole and zinc maleate.

[0083] Example 7: 1 part triflumizole, 0.5 parts zinc succinate (approximately 1 mole of zinc cation and approximately 1 mole of succinic acid per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.2 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cation, and approximately 1 mole of succinate anion). Figure 14 shows the diffraction chart of zinc succinate. Figure 15 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.52°, 9.87°, 10.33°, 15.33°, 18.30°, 19.95°, 20.84°, 21.58°, 22.45°, 23.21°, and 25.52°. The solid product has a different crystal structure from triflumizole and zinc succinate.

[0084] Example 8: 1 part triflumizole, 0.5 parts zinc malonate (approximately 1 mole of zinc cations and 1 mole of malonate anions per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.1 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of malonate anions). Figure 16 shows the diffraction chart of zinc malonate. Figure 17 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.40°, 8.73°, 15.24°, 15.97°, 17.08°, 18.34°, 20.04°, 22.63°, 24.82°, and 30.04°. The solid product had a different crystal structure from triflumizole and zinc malonate.

[0085] Example 9: 1 part triflumizole, 0.7 parts zinc terephthalate (approximately 1 mole of zinc cations and 1 mole of terephthalate anions per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.6 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of terephthalate anions). Figure 18 shows the diffraction chart of zinc terephthalate. Figure 19 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 8.69°, 9.88°, 11.92°, 13.31°, 15.08°, 16.05°, 20.61°, 21.30°, 21.76°, and 25.23°. The solid product had a different crystal structure from triflumizole and zinc terephthalate.

[0086] Example 10: 1 part triflumizole, 0.6 parts zinc glutarate (approximately 1 mole of zinc cations and approximately 1 mole of glutarate anions per mole of triflumizole), and 0.5 parts water were placed in a mortar and ground. 0.2 parts of methanol was added, and the mixture was further ground and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of glutarate anions). Figure 20 shows the diffraction chart of zinc glutarate. Figure 21 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 10.76°, 11.34°, 11.65°, 12.53°, 19.92°, 20.52°, 20.83°, 22.34°, 22.71°, and 24.72°. The solid product had a different crystal structure from triflumizole and zinc glutarate.

[0087] Example 11 1 part of triflumizole, 0.6 parts of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt (approximately 1 mole of zinc cations and approximately 2 moles of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione anions per mole of triflumizole), and 0.5 parts of water were placed in a mortar and pulverized. 0.2 parts of methanol was added to the mixture, which was further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione anions). Figure 22 shows a diffraction chart of 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt. Figure 23 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.89°, 7.62°, 9.89°, 11.32°, 11.71°, 13.31°, 14.82°, 18.62°, 18.90°, 20.44°, 23.23°, and 24.50°. The solid product has a different crystal structure from triflumizole and 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione zinc salt.

[0088] Example 12 1 part of triflumizole, 0.5 parts of 2,6-pyridinedicarboxylic acid (approximately 1 mole of 2,6-pyridinedicarboxylic acid per mole of triflumizole), 0.2 parts of zinc oxide (approximately 1 mole of zinc oxide per mole of triflumizole), and 0.5 parts of water were placed in a mortar and pulverized. 0.1 parts of methanol was added to the mixture, which was then further pulverized and mixed. The mixture was then air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of 2,6-pyridinedicarboxylic acid anions). Figure 24 shows a diffraction chart of 2,6-pyridinedicarboxylic acid. Figure 25 shows a diffraction chart of zinc oxide. Figure 26 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.17°, 10.57°, 11.32°, 13.73°, 14.07°, 17.76°, 19.35°, 20.60°, 20.89°, and 21.75°, and had a crystal structure different from that of triflumizole, 2,6-pyridinedicarboxylic acid, and zinc oxide.

[0089] Example 13: 10 parts of triflumizole, 4.8 parts of phthalic acid (approximately 1 mole of phthalic acid per mole of triflumizole), 2.4 parts of zinc chloride (approximately 1 mole of zinc chloride per mole of triflumizole), 6.4 parts of triethylamine, and 160 parts of methanol were placed in an Erlenmeyer flask and mixed by stirring overnight at room temperature. The resulting solution was filtered to obtain a residue, which was washed with methanol to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 1 mole of phthalate anions). Figure 27 shows the diffraction chart of phthalic acid. Figure 28 shows the diffraction chart of zinc chloride. Figure 29 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 4.94°, 7.49°, 11.18°, 13.89°, 15.07°, 18.46°, 19.56°, 20.32°, 20.68°, and 24.77°. The solid product has a different crystal structure from triflumizole, phthalic acid and zinc chloride.

[0090] Example 14: 0.50 parts of triflumizole, 0.44 parts of zinc dimethyldithiocarbamate (approximately 1 mole of zinc cations and approximately 2 moles of dimethyldithiocarbamate anions per mole of triflumizole), and 20 parts of dichloromethane were placed in a recovery flask and mixed with stirring. The solvent was removed from the resulting liquid using an evaporator to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of dimethyldithiocarbamate anions). Figure 30 shows the diffraction chart of zinc dimethyldithiocarbamate. Figure 31 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.90°, 10.59°, 11.67°, 11.92°, 13.63°, 15.65°, 17.52°, 18.84°, 20.40°, 21.54°, and 24.40°. The solid product has a different crystal structure from triflumizole and zinc dimethyldithiocarbamate.

[0091] Example 15: 1 part triflumizole, 0.7 parts benzoic acid (approximately 2 moles of benzoic acid per mole of triflumizole), 0.3 parts copper(II) hydroxide (approximately 1 mole of copper(II) hydroxide per mole of triflumizole), and 0.3 parts of methanol were placed in a vial and stirred with a stirrer for 1 hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of copper(II) cations, and approximately 2 moles of benzoate anions). Figure 32 shows a diffraction chart of benzoic acid. Figure 33 shows a diffraction chart of copper(II) hydroxide. Figure 34 shows a diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.43°, 6.21°, 9.75°, 12.99°, 14.91°, 14.75°, 17.48°, 19.37°, 21.08°, and 23.58°, and had a crystal structure different from that of triflumizole, benzoic acid, and copper(II) hydroxide.

[0092] Example 16: 1 part triflumizole, 0.4 parts propionic acid (approximately 2 moles of propionic acid per mole of triflumizole), 0.2 parts zinc oxide (approximately 1 mole of zinc oxide per mole of triflumizole), and 0.3 parts methanol were placed in a vial and stirred for 1 hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of propionate anions). Figure 35 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 5.16°, 10.42°, 11.26°, 12.97°, 15.70°, 16.54°, 19.07°, 21.46°, 22.55°, and 26.02°. It had a different crystal structure from triflumizole and zinc oxide.

[0093] Example 17: 1 part triflumizole, 0.4 parts propionic acid (approximately 2 moles of propionic acid per mole of triflumizole), 0.3 parts copper(II) hydroxide (approximately 1 mole of copper(II) hydroxide per mole of triflumizole), and 0.3 parts of methanol were placed in a vial and stirred for 1 hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of copper(II) cations, and approximately 2 moles of propionate anions). Figure 36 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.69°, 9.18°, 12.18°, 13.82°, 17.53°, 18.39°, 19.99°, 20.19°, 22.95°, and 26.06°. The crystal structure was different from that of triflumizole and copper(II) hydroxide.

[0094] Example 18: 1 part triflumizole, 0.5 parts isobutyric acid (approximately 2 moles of isobutyric acid per mole of triflumizole), 0.2 parts zinc oxide (approximately 1 mole of zinc oxide per mole of triflumizole), and 0.3 parts methanol were placed in a vial and stirred for 1 hour. The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of zinc cations, and approximately 2 moles of isobutyric acid anions). Figure 37 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 6.30°, 7.31°, 8.31°, 12.72°, 14.52°, 14.75°, 17.55°, 19.21°, 19.75°, and 21.03°. It had a different crystal structure from triflumizole and zinc oxide.

[0095] Example 19: 1 part triflumizole, 0.5 parts phthalic acid (approximately 1 mole of phthalic acid per mole of triflumizole), and 0.3 parts copper(II) hydroxide (approximately 1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for 1 hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of copper cations, and approximately 1 mole of phthalate anions). Figure 38 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 7.17°, 8.29°, 9.16°, 10.16°, 11.19°, 12.26°, 14.27°, 17.78°, 24.71°, and 28.17°. It had a different crystal structure from triflumizole, phthalic acid, and copper hydroxide.

[0096] Example 20: 1 part triflumizole, 0.5 parts terephthalic acid (approximately 1 mole of terephthalic acid per mole of triflumizole), and 0.3 parts copper(II) hydroxide (approximately 1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for 1 hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of copper cations, and approximately 1 mole of terephthalate anions). Figure 39 shows the diffraction chart of terephthalic acid. Figure 40 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 8.13°, 10.82°, 12.08°, 12.49°, 15.70°, 16.52°, 18.17°, 20.68°, 24.09°, and 27.37°. It had a different crystal structure from triflumizole, terephthalic acid and copper hydroxide.

[0097] Example 21: 1 part triflumizole, 0.3 parts maleic acid (approximately 1 mole of maleic acid per mole of triflumizole), and 0.3 parts copper(II) hydroxide (approximately 1 mole of copper(II) hydroxide per mole of triflumizole) were placed in a vial, 0.4 parts of methanol was added, and the mixture was stirred with a stirrer for 1 hour (at room temperature). The suspension was then filtered and air-dried to obtain a solid product (a complex containing 1 mole of triflumizole, approximately 1 mole of copper cations, and approximately 1 mole of maleate anions). Figure 41 shows the diffraction chart of maleic acid. Figure 42 shows the diffraction chart of the solid product. The solid product had characteristic diffraction peaks at diffraction angles (2θ): 10.90°, 12.27°, 13.17°, 14.15°, 14.68°, 18.42°, 19.01°, 20.16°, 23.34°, and 25.16°. It had a different crystal structure from triflumizole, maleic acid and copper hydroxide.

[0098] In this example, the compositions were evaluated by the following method. [Triflumizole Residual Rate] Using high performance liquid chromatography, the mass (C0) of triflumizole contained in the composition immediately after preparation was measured. The composition was then left to stand in a constant temperature bath at 54°C for two weeks. Using high performance liquid chromatography (HPLC), the mass (C2) of triflumizole contained in the composition after standing for two weeks was measured, and the triflumizole residual rate (a2) was calculated. A higher residual rate (a2) indicates better chemical stability. Triflumizole residual rate a2 (%) = C2 / C0 × 100

[0099] [Particle size] Using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, SALD-2300), the volume-based 50% particle size (d0) of triflumizole in the composition immediately after preparation was measured. The composition was then allowed to stand in a thermostatic chamber at 54°C for 2 weeks. Using a laser diffraction particle size distribution analyzer (Shimadzu Corporation, SALD-2300), the volume-based 50% particle size (d2) of triflumizole in the composition after standing for 2 weeks was measured. A smaller change in particle size indicates better stability.

[0100] Example 22: 16.6 parts of the solid product obtained in Example 13, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinate metal salt, 2 parts of POA allylphenyl ether, 45.6 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed in a container equipped with an agitator and stirred at 50-55°C for 2 hours. The resulting mixture was cooled to room temperature and subjected to a wet-milling treatment to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

[0101] Example 23: 16.6 parts of the solid product obtained in Example 9, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinate metal salt, 2 parts of polyoxyethylene arylphenyl ether ammonium sulfate, 45.6 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed in a container equipped with an agitator and stirred at 50-55°C for 2 hours. The resulting mixture was cooled to room temperature and subjected to a wet-milling process to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

[0102] Example 24: 15.2 parts of the solid product obtained in Example 6, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinate metal salt, 2 parts of polyoxyethylene arylphenyl ether sulfate ammonium salt, 47 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed in a container equipped with an agitator and stirred at room temperature for 30 minutes. The resulting mixture was subjected to wet grinding to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to the suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

[0103] Comparative Example 1: 10 parts of triflumizole, 5 parts of antifreeze, 0.5 parts of dioctyl sulfosuccinate metal salt, 2 parts of polyoxyethylene arylphenyl ether sulfate ammonium salt, 52.2 parts of water, 0.2 parts of antifoaming agent, and 0.1 parts of preservative were placed in a container equipped with an agitator and stirred for 2 hours. The resulting mixture was subjected to wet grinding to obtain a suspension. A mixture consisting of 0.3 parts of thickener, 29.6 parts of water, and 0.1 parts of preservative was added to this suspension and mixed to obtain a composition. The evaluation results of the composition are shown in Table 1.

[0104]

Claims

1. An organometallic complex consisting of triflumizole, a metal cation and an organic acid anion.

2. The organometallic complex according to claim 1, wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese.

3. The organometallic complex according to claim 1 or 2, wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

4. A method for producing an organometallic complex consisting of triflumizole, a metal cation and an organic acid anion, comprising mixing triflumizole and / or a salt thereof with at least one selected from the group consisting of an organic acid metal salt, a combination of an organic acid and a metal compound, and a combination of an organic acid salt and a metal compound.

5. The method according to claim 4, wherein the molar ratio during mixing is 0.5 to 2 moles of metal cations derived from the metal compound and 0.25 to 4 moles of organic acid anions derived from the organic acid and / or organic acid salt, per 1 mole of triflumizole derived from triflumizole and / or a salt thereof.

6. The method according to claim 4 or 5, wherein the metal element of the metal cation is one selected from the group consisting of zinc, copper, magnesium, calcium, nickel, cobalt, iron and manganese.

7. The method according to claim 4 or 5, wherein the organic acid of the organic acid anion is at least one selected from the group consisting of acetylacetone and its tautomers, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, benzoic acid, phthalic acid, terephthalic acid, 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione and its tautomers, 2,6-pyridinedicarboxylic acid, dimethyldithiocarbamic acid, diethyldithiocarbamic acid, N-ethyl-N-phenyldithiocarbamic acid, propionic acid, and isobutyric acid.

8. A composition comprising triflumizole, an organometallic complex consisting of a metal cation and an organic acid anion.

9. A composition comprising triflumizole, an organometallic complex consisting of a metal cation and an organic acid anion, and water.

10. An agricultural and horticultural fungicide containing as an active ingredient an organometallic complex consisting of triflumizole, a metal cation and an organic acid anion.

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